Bleaching methods and agent



1-,; action, itintroduces a non-food: constituent into the-bleached product -a'nd is, therefore," "not asdesirable asa peroxidethatitself forms Patented Apr. 19, 1932 tu u wan PATENT JJQFEIjCiE FPHILIRE. ROLLHAUS, ;-OE :EKST ORANGE, NEW JERSEY, AND WILLIIAM B. STODDARD,,,OF F 1 STAMEOBD; CONNECTICUT, ASSIGNORS TO PILOT LABORATORY, INC OEARLINGTON; :NEWEJ'ERSEYZ, A CORPORATION OF NEW JERSEY BLEAGHING'NETHODS AND AGENT No Drawing.

; Ouriinvention relates to a process :of andagent for bleaching organic matterasuch as z food :zstufis jot 5.21111 111511 zorsvegetablee orlgln,

waxes andthelikepand relates morepartmu- 'lrlarlyto a :processnfi and urgent:- for bleachin {2;

rrandiefficient in: itsriactionbthatathere is re-' 1' quired: only art smallrzquanti-ty, (too: minute to bet-noticeable innthe bleached product; but 1 11 11180311 agent-that shall not, itself; be deleterwiousi on harmful. .Thus,;" the common inori'aganicsibleachingsagents,asuch aschlorine and Anitrogen.10Xidesyalthoughscheap and efiicientv -;"are'=1- ObjECtlOIIEblQibQCEIUSfl. of: their harmful rnature inrtoodsaornfoodproducts. :Benzoyl T i'peroiideathou-gh relatively-wary e pens1ve= as ucomparedi vvith inorganic LbleaCh1I1g agents,

ahasstherefore,abeen rusedwforzthe. bleaching fof siflour': :and nther *fobd products. I,;It=.1S',-l1'OW rever;cnot ienly rzexpensive; abutnbelongs to, a

classrot; SUbSfifiHQGSTthGF useofx-Which: in==food -i stut'fsthasvbeen': considered harmfuland has, itherefor,ebeentrestricted.a Moreover, as the solubility fofibenzoylzperoxide in fats and 011s 302 is snegligi-blerorweryfislight, its effectiveness z foribleaehingsubstances in WHIChZlIhG'COlOIlIIg :mconstituent isticontained 1n: an o1lyor- Waxy.

vvehiclm; is acorrespondingly limited. Furithermore, asr benzoylkperoxidetdoes not-rform a food product as the result of the bleaching a -food productasthe result-of the-bleaching action.

:An obj ectofour present inventionis; therefore; to 'provide'an inexpensivafeffective and eficient bleaching agent that is applicable to food stuffs and that does notintroduce or leave adeleterious.substancein the bleached product. a

. Anotherriobjecti ofnour .invention is to: provide a bleaching agent in-the n'ature of aztood fEOLPIlOdUl Ct orrthat as a resulttofithelbleaching Application filed 'November 12, 1928.

' OXlClS.

7 smaller quantity of the bleachingaagent is 1 required for a given bleaching-action.

Serial No. 319,002.

act-ion, forms foodproduct in the; bleached material.

7 Further objects and featuresof theinven- :tion are to activates-11d rendenmore-active and efficient for thebleachingot:fdod:stufi'sg' peroxidized food, materials or=-peroxidsof the higher fatty acids, ELDdLtOHPIOVldQZGlIIlproved methods for"; the bleaching 10f zifood products by means-of activated-organic per- In accordance With our invention, ai-halogen derivative ofan organicrperoliid, :and particularly a halogen derivative; or derivatives of a fatty acidperoxide, or of mixture of fatty acid peroxids, are :formed andused for bleaching flour and other millingor. toocl products. Through the substitution 0f a halogen, such l as chlorine; ,for a hydrogen atom of the fatty acidwperoxide, the peroxid is-rendered much more-active and-tnioreieifi cient; 1n proportion to --1ts actlve 0Xygen,:=content than is the unsubstltuted-wperoxlcl. A Any halogen ,derivativei'of a :fatty acid peroxid, or: mlxture of -=der1vat1ves Lof such peroxids,

may be employed, Ai'chlorinetderivative is? Y5 however, preierredl Theymixedifattygacids produced from the fattyacid content :of a

naturally occurringfator oilyas foriexample.

v-cocoanut oil, are particularly 'suited'aast a .source of the substituted organiccperoxidspfi aspGIOXldS made fromnthese naturallycoccurring fats are not onlynlessexpensiveithan peroxids made from 2' the: r individualnfatty acidsthat are commerciallyavailable forrex ample, oleic or stearic acid but,'as they:lravea lower average molecular Weight: than: that of the. individuah fatty acids commercially available, the peroxids have ahigher. percent age of active -yoxygen. Consequently; a

The halogen derivativescf-the, fatty: acid wperoxids are not only active :and GlHQLlGIll'ROKldizingand bleaching ,agents,- but-arela'lso 1 soluble in oils and fats. This israniadvantage inasmuch as 1 the coloring matters; that are) to -be.-oxidized by the: bleaching agent; are;-frccessible to agents insoluble in fats. By dissolving in a common solvent with the coloring constituents, the active peroxids are brought into intimate cont-act therewith for the most efficient action.

In bleaching a substance such as flour, with a halogen substituted fatty acid peroxid or a mixture of halogen substituted fatty acid peroxids, the peroxid may be sprayed directly in a finely divided condition into the flour or, it may be dissolved in an oil solvent and sprayed into the flour as described in co-pending application Serial No. 314,545.

The halogen peroxid derivatives or mixture of derivatives for use in accordance with our invention may be formed in any suitable manner. I11 the preferred form of the invention, however, chlorinated acid chlorides are formed from the fatty acid and is then peroxidized by a suitable peroxidizing agent. In forming chlorinated acid chlorides from cocoanut oil fatty acids having an average molecular weight of 205, 615 parts by weight of the fatty acid, equivalent to 3 moles of the fatty acid, are mixed with about 206 parts by weight of phosphorous trichloride and allowed to stand for about 48 hours, at room temperature, to essentially complete the reaction. It will be understood that when acids or other molecular weights are used, the proportion of fatty acid will be varied accordingly. The separated phosphorous acid is then removed from the acid chloride product. The acid chloride product, the weight of which will now have been increased to about 715 parts through the absorption of chlorine, is cooled with ice, and chlorine is passed into it until the product gains in weight about 15%, i. e., 113 parts, the total weight of the product increasing to 828 parts. The temperature during this chlorination should be near 0 0., and preferably should not exceed about 30 C. The product is a fatty acid chloride having its chain chlorinated to about 15%. The chlorine is attached principally to the alpha carbon atom,

that is, the carbon atom adjacent to the carboxyl chloride group. The chlorinated acid chloride thus obtained is peroxidized in the following manner and proportion:

In a vessel fitted with an agitator, 700 cc. of 7.5% hydrogen peroxide are placed. To this is added 1 litre of 1% soap solution. The mixed solution is cooled to 0 C., by chipped ice. To this are added simultaneously 309 grams of the above chlorinated acid chloride and 245 cc. of caustic soda solution containing 342.6 grams of NaOH per litre. The mixture is continuously agitated for about seven minutes or, until the odor of acid chloride disappears, the temperature being kept near 0 C., by the continued addition of chipped ice. The reaction product is then acidified and the oily peroxid is separated from the water. It may then be taken up in a mineral oil solvent, if desired. The peroxid is dried with anhydrous magnesium sulphate, or a similar drying material, and is filtered or decanted, when it is ready as a bleaching composition.

The mixture of chlorinated fatty acid peroxide or peroxides, either alone or dissolved in a mineral oil solvent, as described in a copending application Serial No. 314,545, is intimately'mixed with the flour by spraying, or any other suitable manner and, in somewhat less proportion than would be required if unchlorinated fatty acid peroxids are used. The treated flour is allowed to stand, at room temperature, for about 48 to 96 hours, at the end of which time it will be found efiiciently bleached.

The halogenated fatty acid peroxids, as well as their mineral oil solutions, have a lower melting point than the corresponding unsubstituted or non-halogenated pe-roxids. This is of advantage in that it permits the substituted peroxids to be sprayed as liquids in cold weather at temperatures at which the unsubstituted or non-halogenated peroxidswould solidify.

The fatty acid peroxids are relatively easy and safe to make and handle. They are more readily soluble in oils than other organic peroxide and are, therefore, particu-- larly well suited for the bleaching of oils or of other materials the coloring matter of which is dissolved or contained in the oily constituents of such material, as for example, in flour, seed meals, egg yolk and the like. Furthermore, the chlorinated fatty acid peroxids, after their bleaching action, leave a residue which is a harmless food product, the chlorine being not free, but combined in the fatty acid. The stability of the peroxid is somewhat greater when saturated, or substantially saturated fatty acids, or hydrogenated cocoanut oil fatty acids are used as the source of the chlorinated fatty acid peroxid and saturated fatty acids are, therefore, preferable for this reason. If unsaturated fatty acids are to be used, they may be saturated by chlorine, or equivalent, before being used for the preparation of the peroxid.

As changes of operation could be made within the scope of our invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

Having now described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A halogenated peroxide of a soap forming fatty acid.

2. A chlorinated peroxide of a soap forming fatty acid.

3. A mixture of peroxide of the halogenated substitution products of the fatty acids contained in a natural fatty material.

4. A mixture of peroxides of the halogen substitution products of the fatty acids occurring in cocoanut oil.

5. A mixture of peroxides of the chlorine substitution products of the fatty acids occurring in cocoanut oil.

6. A process of forming a bleaching agent which comprises peroxidizing a chlorinated fatty acid chloride.

7 A process of forming an activated product of the type described which comprises forming a halogenated fatty acid chloride, and peroxidizing said chloride.

8. A process of forming an activated product of the type described which comprises treating a fatty acid chloride with chlorine to form a chlorine substitution product, and peroxidizing said substitution product.

9. A process for forming a bleaching agent which comprises peroxidizing a mixture of the chlorinated chlorides of cocoanut oil fatty acids.

10. A process of forming an activated product of the type described which comprises treating a mixture of the acid chlorides of cocoanut oil fatty acids with chlorine to form a mixture of chlorine substitution products, and peroxidizing said substitution products in said mixture.

In Witness whereof We have hereunto set our hands this 9th day of November, 1928.

PHILIP E. ROLLHAUS. WILLIAM B. STODDARD. 

